Phase change ink formulations, colorant formulations, and methods of forming colorants

ABSTRACT

The invention encompasses a compound having the formula:  
                 
 
wherein R 1 , Z and the carbonyl can be comprised by a common ring, wherein R 1  comprises a chromophore that absorbs light from the visible wavelength range, and wherein n is an integer that is at least 12. The invention also encompasses a solid phase change ink composition. Such composition includes a phase change ink carrier and a colorant. The colorant comprises a chromophore that absorbs light from the visible wavelength range, and has the formula:  
                 
 
wherein R 1 , Z and the carbonyl can be comprised by a common ring, wherein n is an integer that is at least 12. Additionally, the invention encompasses a method of forming a colorant. A first compound having the formula,  
                 
 
is reacted with a second compound having the formula Z(CH 2 ) n CH 3 , wherein n is an integer that is at least 12, to form a third compound having the formula,  
                 
wherein the third compound comprises a chromophore that absorbs light from the visible wavelength range.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. patent applicationSer. No. 09/772,617, filed Jan. 30, 2001; which is in turn a divisionalapplication of U.S. patent application Ser. No. 09/397,348 (now U.S.Pat. No. 6,235,094), filed Sep. 15, 1999; which is in turn acontinuation-in-part application of U.S. patent application Ser. No.09/023,851 (now U.S. Pat. No. 6,028,138), filed on Feb. 13, 1998; whichis in turn a continuation-in-part application of U.S. patent applicationSer. No. 08/672,815 (now U.S. Pat. No. 5,830,942), filed on Jun. 28,1996 and U.S. patent application Ser. No. 09/013,410 (now U.S. Pat. No.5,994,453), filed Jun. 28, 1996.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The invention relates to new colorant compositions, and to methods offorming and using such colorants. In particular applications, theinvention pertains to phase change ink formulations.

2. Description of the Relevant Art

The present invention encompasses new colorant compounds, routes totheir preparation, and methodology for incorporating such compounds intophase change inks. Phase change inks are compositions which are in asolid phase at ambient temperature, but which exist in a liquid phase atan elevated operating temperature of an ink jet printing device. At thejet operating temperature, droplets of liquid ink are ejected from theprinting device. When the ink droplets contact the surface of a printingmedia, they solidify to form a printed pattern. Phase change inkmethodology is described generally in U.S. Pat. Nos. 4,889,560;5,372,852 and 5,827,918.

A definition which will be adopted in this disclosure and the claimsthat follow will be to utilize the term “colorant” to refer to modifieddyes, chromophores and pigments which are suitable for inclusion inphase change inks. Another definition which will be adopted in thisdisclosure and the claims that follow will be to refer to a phase changeink composition as comprising a colorant and a carrier. The term“carrier” is to be understood to comprise all components of a phasechange ink composition with the exception of the colorant. In phasechange ink compositions comprising more than one colorant, the carrierwill include everything except a particular colorant of interest, andcan, therefore, comprise colorants other than that which is of interest.

A difficulty associated with phase change inks can be in solubilizingtraditionally utilized dyes, chromophores and pigments. Many coloredcompounds useful in producing phase change inks for digital printinggenerally comprise polar functional groups, and accordingly areinsoluble in the organic carrier of a phase change ink composition. Thesolubility of the colored compounds can be improved by increasing thehydrophobic character of the colored compounds. Accordingly, it isdesirable to develop methods for increasing the hydrophobic character ofexisting chromophores, dyes and pigments to produce new coloredcompounds, as well as to develop new colorants with substantialhydrophobic character.

BRIEF SUMMARY OF THE INVENTION

In one aspect, the invention encompasses a compound having the formula:

wherein R₁ comprises a chromophore that absorbs light from the visiblewavelength range, and wherein n is an integer that is at least 12.

In another aspect, the invention encompasses a solid phase change inkcomposition. Such composition includes a phase change ink carrier and acolorant. The colorant comprises a chromophore that absorbs light fromthe visible wavelength range, and has the formula:

wherein n is an integer that is at least 12.

In yet another aspect, the invention encompasses a method of forming acolorant. A first compound having the formula,

is reacted with a second compound having the formula Z(CH₂)_(n)CH₃,wherein n is an integer that is at least 12, to form a third compoundhaving the formula,

wherein the third compound comprises a chromophore that absorbs lightfrom the visible wavelength range and is soluble in a phase change ink.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a generalized reaction scheme comprising methodology of thepresent invention.

FIG. 2 shows a generalized reaction scheme of a net overall reactioncomprising methodology of the present invention.

FIG. 3 shows yet another generalized reaction scheme of a net overallreaction comprising methodology of the present invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The invention comprises new colorants, as well as new phase change inkcompositions comprising the colorants. The new colorants have asubstantial amount of hydrophobic character. In one aspect, thehydrophobic character is imparted by incorporating at least one alkyl oralkoxylate chain that is at least 13 carbon units long into colorants ofthe present invention. In particular embodiments, the alkyl oralkoxylate chain is at least 20 carbon units long, and in otherembodiments at least 40 carbon units long. It can be preferred that thenumber of carbon atoms in the alkyl or alkoxylate chain not exceed about300, as such long carbon chains (if present in sufficient concentration)can increase a melting point of a phase change ink beyond a desiredlimit of about 170° C. Of course, if a colorant is provided to asufficiently low concentration in a phase change ink such that carbonchains comprising greater than 300 carbon units do not adversely affecta melting point of the ink, the preferability of having less than 300carbon units is diminished. Also, it is noted that eutectic mixturescomprising a colorant can lower a melting point of the colorant so thata melting point of the colorant can be less than or equal to 170° C.even if the colorant has chains with more than 300 carbon units.Consequently, it is noted that a melting point temperature of a phasechange ink can be engineered even from colorants having melting pointssignificantly different than that ultimately desired in the phase changeink.

A general formula for one class of colorant encompassed by the presentinvention is shown below as compound 1.

The group R₁ of compound 1 comprises a chromophore that absorbs lightfrom the visible wavelength range (i.e., light having a wavelength offrom about 400 nanometers to about 750 nanometers). The label n ofcompound 1 represents an integer that is at least 12. In preferredembodiments, n is at least 17. In further preferred embodiments(particularly where the colorant is provided in high concentration in aphase change ink, with high concentration being defined as aconcentration greater than about 25% (by weight) of the ink), n is lessthan or equal to 299. The segment Z of compound 1 comprises one or moreatoms; and comprises an atom selected from group IV of the periodictable (i.e., the group comprising carbon), group V of the periodic table(i.e., the group comprising nitrogen) or group VI of the periodic table(i.e., the group comprising oxygen and sulphur).

Although the compound 1 is shown in a linear form, it is to beunderstood that compound 1 can be comprised by a cyclic structure (i.e.,compound 1 can be a portion of a cyclic structure), and that thecarbonyl, R₁ and Z can be contained in a common ring of such cyclicstructure. Compound 1A shows a dashed line to indicate the ring of acyclic structure of compound 1.

In particular embodiments, the segment Z(CH₂)_(n)CH₃ of compound 1 iseither group 2 (below) or group 3 (below).NH(CH₂)_(n)CH₃   2.CH₃(CH₂)_(n)—N—(CH₂)_(y)CH₃   3.In group 3, the label y is an integer that can be the same or differentthan n, and which is preferably greater than 12, although it can bezero. The amines (or generally a nucleophile) of groups 2 and 3correspond to the component Z of compound 1.

The segment R₁ of compound 1 comprises carbon, and can comprise, forexample, aryl moieties in color-yielding combinations. Exemplary arylmoieties are phenyl and naphthyl. The segment R₁ and the carbonyl ofcompound 1 can together comprise a chemical group selected from thegroup consisting of ester, lactone, amide, lactam and imide. Further, R₁and the carbonyl of compound 1 can together comprise an auxochrome. Thegroup R₁ can also comprise an auxochrome by itself by containingelectron donating groups or electron withdrawing groups.

Further, the group R₁ of compound 1 preferably comprises a chromophorethat absorbs light within the visible wavelength range such thatcompound 1 can be a suitable colorant for a phase change ink. Among thepreferred chromophores for phase change inks are chromophorescorresponding to cyan, magenta, yellow or black colors. The chromophoreencompassed by the compound 1 can comprise, for example, methine, metalphthalocyanine, metal phthalocyanine, azamethine, azo, triphenylmethane,rhodamine, xanthene, indoaniline, pyridone, perylene, anthrapyridone andanthraquinone.

In an exemplary embodiment, compound 1 can have a formula correspondingto that of compound 4 (shown below).

The components R₅₀, R₅₁, R₅₂, and R₅₃ of compound 4 can, for example, beselected from the group consisting of hydrogen, halogens, hydroxygroups, alkoxy groups, trifluoromethyl groups, and alkyl groups, and canbe the same as one another or different than one another. The componentsR₇ and R₈ of compound 4 are selected from the group consisting ofhydrogen and carbon-containing materials, and can be, for example, alkylmoieties, aryl moieties or hydrogen. Components R₇ and R₈ can be thesame or different relative to one another, and can be comprised by acommon ring. In particular embodiments, at least one of the componentsR₇ and R₈ of compound 4 can comprise a chain having the formula ofmaterial 5.

In material 5, j is an integer of from 0 to about 300 (preferably from 0to 100, and more preferably from 1 to 10), and the representation of“(Q, H)” indicates that either a substituent Q or a hydrogen can be inthe shown positions. Substituent Q represents either an alkyl group oran aryl group, and can vary amongst different alkyl and aryl groupswithin either or both of components R₇ and R₈. In particularembodiments, Q is CH₃ throughout both of R₇ and R₈.

A compound corresponding to compound 4, and having R₇ and R₈corresponding to the formula of material 5, can be formed according tothe reaction scheme shown in FIG. 1. Specifically, aniline isalkoxylated to yield anilined 252 (shorthand for aniline with 2 moles ofethylene oxide (EO), 5 moles of propylene oxide (PO) and 2 moles of EOto yield a block co-polymer). The aniline 252 of FIG. 1 corresponds to acombination of aniline and a pair of polymers encompassed by material 5,with the polymer encompassed by material 5 having the formula shownbelow as 5A (i.e., a 1:2.5:1 structure).

The 2.5 of material 5A indicates that on average there are 2.5 of theCH₂CH(CH₃)O units in a chain. Of course, in any given chain, the actualnumber of such units will be an integer amount (typically 2 or 3).

After formation of the aniline 252 in the FIG. 1 reaction process, theaniline 252 is acetylated. After the acetylation, a resulting aniline252 diacetate is converted to an aldehyde by a Vilsmeier-Haack reactionutilizing phosphorus oxychloride and N,N-dimethylformamide (DMF). Basichydrolysis of the acetate protecting groups is accomplished with warmdilute sodium hydroxide containing a small percentage of potassiumhydroxide. The benzaldehyde derivative containing the free hydroxylgroups on the alkoxylate chain is neutralized, phased by warming toabove the cloud point, and allowed to stand and separate. The salt layeris removed and the resulting aldehyde layer is reduced in vacuo to yieldthe anhydrous precursor of a chromophore. The aldehyde is then condensedwith a cyanoacetate derivative to form the resulting exemplary colorantof the present invention.

Other epoxides can be utilized instead of, or in addition to, the EO andPO epoxides discussed above. For instance, butylene oxide (BO) and/orstyrene oxide (SO) can also be utilized.

The reaction chemistry shown in FIG. 1 is an example of a condensationreaction encompassed by the present invention. A more generaldescription of condensation reactions of the present invention is afollows. First, a starting material 10 (shown below, and referred tohereafter as “compound 10”) is provided.

The segment A of compound 10 is an aromatic ring, and the group R₄ ofcompound 10 comprises one or both of carbon and hydrogen. Compound 10 isreacted with a cyanoacetate derivative 11 having the formula shownbelow.

The label “n” of cyanoacetate derivative 11 represents an integer, andis preferably at least 12.

Condensation of aldehyde compound 10 with cyanoacetate derivative 11forms a product having formula 12.

Compound 12 is a methine colorant, and an exemplary compound encompassedby the present invention. In a particular embodiment of the invention,compound 11 comprises a stearyl amide of cyanoacetic acid, and compound10 comprises N,N-dialkyl amino benzaldehyde. Condensation of compounds10 and 11 yields a compound 12 corresponding to a methine yellowcolorant.

Methine dyes and pigments represent an important class of chromogen invirtually every area requiring a yellow to cyan hue. Numerousderivatives have been made and have been used to make many types of dyes(e.g., dispersed, acid, reactive, etc.). Some shortcomings of prior artmethine dyes in hot melt wax systems (i.e., phase change ink systems)are due to solubility and blooming problems. These arise from therelatively small and compact structure of prior art methine dyes.Because of their structures, aggregation of dye moieties readily takesplace. Such aggregation can lead to solubility problems (aggregatedmolecules can combine and form precipitates which can adversely affectprinthead performance), as well as to blooming if the unaggregatedmolecules migrate to the surface of a printed image.

An advantage of the present invention is that it encompasses syntheticmethods which can be utilized to create methine colorants whileovercoming the manufacturing and preparation disadvantages associatedwith prior art methine dye preparation (i.e., the use of hazardousand/or volatile solvents and elaborate purification procedures).Specifically, reactions of the present invention are preferably runwithout traditional volatile organic solvents. Instead, the reactionsare preferably run at temperatures that allow each component, eachintermediate, and each final product to be molten. Accordingly, thereaction mixture functions as its own solvent, and no additionalsolvents are needed. Suitably high temperatures are employed to keep thereaction molten during its duration, as well as to allow water and/orlow molecular weight alcohols to be removed. Example 1 describes anexemplary colorant preparation procedure encompassed by the presentinvention. The colorant obtained from the process of Example 1 has aviscosity similar to the desired viscosity of a final ink, and could,accordingly, be utilized as ink directly, rather than being utilized incombination with a carrier. However, the colorant was tested forsuitability in phase change ink applications by combining the colorantwith a phase change ink carrier solution. Specifically, the colorant wascombined with an ink base, filtered and printed (see Example 2 forpreparation of the ink base, and Example 3 for combination of thecolorant and ink base).

The method described above with reference to compounds 10-12 utilized acyanoacetate derivative having an alkyl chain with at least 13 carbonatoms incorporated therein (compound 11). Another method encompassed bythe present invention is to utilize a cyanoacetate derivative which doesnot have the alkyl chain with at least 13 carbon atoms alreadyincorporated therein, but which can be subsequently reacted toincorporate an alkyl group having at least 13 carbon atoms. Forinstance, the compound 10 which was discussed above can be reacted witha second compound 13, to form a third compound 14.

Compound 14 can be subsequently reacted with NH₂(CH₂)_(n)CH₃ to form thecompound 12 that was discussed above. While the invention is not limitedby the process order for introducing the alkyl group feature, a specificadvantage of the invention can be to prepare a new colorant throughsolventless transformation in a molten state.

An exemplary material for compound 10 is shown below as compound 15.

The components R₅₆, R₅₇, R₅₉, and R₅₉ of compound 10 can, for example,be selected from the group consisting of hydrogen, halogens, hydroxygroups, alkoxy groups, trifluoromethyl groups, and alkyl groups, and canbe the same as one another or different than one another. The componentsR₇ and R₈ of compound 15 are selected from the group consisting ofhydrogen and carbon-containing materials, and can be, for example, alkylmoieties, aryl moieties or hydrogen. Components R₇ and R₈ can be thesame or different relative to one another, and can be comprised by acommon ring. In particular embodiments, at least one of R₇ and R₁comprises a chain having the formula of material 5, wherein j is aninteger from 0 to about 300, and wherein Q is hydrogen or CH₃, and canvary between hydrogen and CH₃ within the chain to yield blockco-polymers.

Another composition which can be formed by methodology similar to thatshown in FIG. 1 is compound 6 (below). An exemplary material encompassedby the formula of compound 6 can be formed by the methodology shown inFIG. 2.

The components R₆₀, R₆₁, R₆₂, R₆₃, R₆₄, R₆₅, R₆₆, R₆₇, R₆₈, R₆₉, R₇₀,and R₇₁ of compound 6 can, for example, be selected from the groupconsisting of hydrogen, halogens, hydroxy groups, alkoxy groups,trifluoromethyl groups, and alkyl groups, and can be the same as oneanother or different than one another. The components R₁₀, R₁₁, R₁₂,R₁₃, R₁₄ and R₁₅ of compound 6 are selected from the group consisting ofhydrogen and carbon-containing materials, and can be, for example, alkylmoieties, aryl moieties or hydrogen. Components R₁₀, R₁₁, R₁₂, R₁₃, R₁₄and R₁₅ can be the same or different relative to one another. Inparticular embodiments, at least one of the groups R₁₀, R₁₁, R₁₂, R₁₃,R₁₄ and R₁₅ can comprise a chain having the formula of material 5. Thelabels “a”, “b”, and “c” of compound 6 are integers of from 1 to 300,and preferably from 1 to 100, and more preferably of from 1 to 10, andcan be the same or different from one another.

The FIG. 2 reaction scheme shows a method of forming an exemplarycompound 6 having “a”, “b” and “c” equal to 2, and R₆₀-R₇₁ as hydrogen.The resulting compound has a significant amount of hydrophobic characterdue to the three carbon tethers (which are linked in the common startingmaterial tris-triethylamino amine, and joined with a common nitrogenmolecule). (The term “tether” is used herein to refer to an organiclinkage between two components.) Compound 6 is an exemplary compound ofthe present invention. Materials other than compound 6 can be formed bysubstituting other molecules for the tris-triethylamino amine of FIG. 2.Such other molecules can comprise longer carbon chains thantris-triethylamino amine, and more than the three tethers oftris-triethylamino amine. Also, the nitrogen nucleophiles of thetris-triethylamino amine can be replaced with other nucleophiles (suchas, for example, oxygen or sulfur), such that one or more of the amidelinkages shown in compound 6 is replaced by a different type of linkage(such as, for example, an ester or a thioester). Additionally, thecentral amine of triethylamino amine can be replaced with a differentatom, such as, for example carbon. A starting material that can besubstituted for the tris-triethylamino amine, and which comprises acentral carbon atom instead of the central nitrogen oftris-triethylamino amine, is a T-SERIES JEFFAMINE™ (available fromHuntsman Chemical of Austin, Tex.). Another exemplary starting materialwhich could be substituted for tris-triethylamino amine is polyethyleneimine, TETRONIC™ (available from BASF Corporation of Parsippany, N.J.).Yet another exemplary starting material is a material comprising acombination of two or more of T-SERIES JEFFAMINE™, polyethylene imine,and tris-triethylamino amine.

In light of the above-discussed substitutions for the tris-triethylaminoamine utilized during formation of compound 6, it will be recognizedthat compound 6 is but one representative of a class of compoundsencompassed by the present invention. Such class comprises at least twosegments having the formula 20 shown below, with the at least twosegments being joined through a common central atom or multi-atomstructure. If the at least two segments are joined through a commonatom, such atom can be either carbon, sulfur, phosphorus or nitrogen. Insegment 20, R₂₀ and R₂₁, comprise one or both of carbon and hydrogen; Z₅comprises carbon, nitrogen, oxygen or sulfur; the components R₇₃, R₇₄,R₇₅, and R₇₆ can, for example, be selected from the group consisting ofhydrogen, halogens, hydroxy groups, alkoxy groups, trifluoromethylgroups, and alkyl groups, and can be the same as one another ordifferent than one another; and b is an integer of from 1 to 300, andpreferably of from 2 to 20. Another way of describing a compound havingat least two segments 20 is shown as compound 21 (below), wherein Gcorresponds to a common central atom or multi-atom structure that joinsthe segments, wherein Z₅, b, R₂₀ and R₂₁ can be the same or different atdifferent segments within the compound, and wherein d is at least 2. Inparticular embodiments, a compound of the present invention has at leastthree segments having the formula 20, and accordingly, d of compound 21is an integer that is at least 3.

It is noted that compound 6 can be reacted with organic acids, mineralacids, or combinations of organic and mineral acids, to protonate one ormore of the amines and accordingly form ion pairs comprising theprotonated compounds and negative counterions. Exemplary acids arestearic acid, hydrochloric acid, sulfuric acid, and dodecyl benzenesulfonic acid. The ion pairs formed from compound 6 and the acids canconstitute colorants having high molecular weights and desirednon-blooming, non-migrating properties in phase change inks. This aspectof the invention can provide a route to materials which exhibitsolubilized pigment behavior.

The above-described materials (materials 1-6, 10-15, 20 and 21) can beutilized as colorants in phase change inks. Accordingly, the materialscan be combined with a phase change ink carrier to form a phase changeink composition. Preferably, the materials will be present in the inkcomposition to a concentration of from about 0.5% to about 60%, and mostpreferably between 5% and 30%. In the particular cases wherein thecolorants have appropriate viscosity and melting temperature to provideprintable properties at a printhead operating temperature, a phasechange ink can consist essentially of the colorant (i.e., the phasechange ink will be essentially pure colorant, and accordingly have nocarrier).

The methods described above with reference to FIGS. 1 and 2 areexemplary methods for forming compounds encompassed by the presentinvention. Another exemplary method is shown in FIG. 3. Specifically,FIG. 3 shows that a first compound “A” (which has a carbonyl attached toa leaving group X) is reacted with a second compound “B” (which has acomponent Z bonded to a carbon-containing group R₂) to form a thirdcompound “C”. In particular aspects of the invention, the group R₂ cancomprise an alkyl chain having at least 13 carbon atoms. In otherembodiments, the group R₂ can comprise a component suitable forsubsequent bonding with an alkyl group having at least 13 carbon atoms.The reaction effectively substitutes group X with the group ZR₂. Thegroup X can comprise, for example, O(CH₂)_(m)CH₃, with m being aninteger of from 0 to 10. Preferably, m is an integer of from 0 to 2. Thecomponent Z can comprise, for example, a nucleophile, such as oxygen,sulphur or nitrogen. In particular embodiments of the invention, thematerial Z-R₂ comprises either of compounds 7 or 8, with n an y beingintegers which are preferably at least 12.

In a further particular embodiment, compound “A” of FIG. 3 can comprisethe carbocation shown below as compound 9.

The components R₈₀, R₈₁, R₈₂, R₈₃, R₈₄, R₈₅, R₈₆, R₈₇, R₈₈, and R₈₉ ofcompound 9 can, for example, be selected from the group consisting ofhydrogen, halogens, hydroxy groups, alkoxy groups, trifluoromethylgroups, and alkyl groups, and can be the same as one another ordifferent than one another. The components R₃, R₄, R₅ and R₆ of compound9 can be selected from the group consisting of hydrogen andcarbon-containing materials, and can be, for example, alkyl moieties,aryl moieties or hydrogen. Further, the groups R₃, R₄, R₅ and R₆ ofcompound 9 can be the same or different than one another.

The reaction of FIG. 3 can comprise, for example, analkylamino-de-alkoxylation reaction which is utilized to add a carbonchain (such as, for example, a stearyl group) to a chromophore. Theaddition of a suitable carbon chain can form a colorant having improvedproperties for utilization in a phase change ink relative to thestarting chromophore. For instance, the addition of a suitable carbonchain can form a colorant having increased molecular weight, enhancedsolubility in an ink base (decreasing the blooming tendency) anddecreased tendency to migrate, relative to the starting chromophore.

An exemplary chromophore which can be treated byalkylamino-de-alkoxylation is INTRATHERM YELLOW P-346™, available fromCrompton and Knowles. INTRATHERM YELLOW P-346™ provides a bright yellowcolor when formulated into phase change ink bases. In addition, the dyeshows good lightfastness and good thermal stability compared toconventional yellow colorants. Unfortunately, at dye loads much above 1%the dye has a tendency to “bloom” to the surface of a test print. Inaddition, the dye tends to migrate under tape and lamination media. Analkylamino-de-alkoxylation transformation encompassed by the presentinvention can improve the performance of INTRATHERM YELLOW P-346™ inphase change inks. For instance, Example 4 (below), together with thedata following Example 4, shows that modification of INTRATHERM YELLOWP-346™ in accordance with the present invention can enhance the imagestability of printed phase change test images relative to unmodifiedINTRATHERM YELLOW P-346™. Further, although the example modification isrelative to INTRATHERM YELLOW P-346™, the procedure of the presentinvention can be readily utilized on a large number of chromophores toenhance their solubility and migration fastness in phase change inks,and accordingly, the commercialization potential of such chromophores issignificantly increased. This feature of the invention is alsoapplicable for the preparation of solvent soluble colorants from dyestypically insoluble in organic carriers.

Exemplary embodiments of the present invention are described in theExamples below. It is to be understood, however, that the Examples areprovided for illustration purposes only. The invention is to be limitedonly by the claims which follow, and not by the chemistry shown in thefollowing Examples except to the extent that such chemistry is expresslyrecited in the following claims.

EXAMPLE 1

Octadecyl amine¹ (about 135.9 grams (0.505 moles)) was carefully heatedin a one-liter four-neck resin kettle equipped with a Trubore stirrer,thermocouple-temperature controller, N₂ atmosphere, and vacuum adapterto about 80° C., at which time it became molten and agitation was begun.Once the octadecyl amine was molten, about 50.0 grams (0.505 moles) ofmethyl cyanoacetate² was slowly added. When the addition was complete,the temperature was held at about 90° C. for approximately 45 minutesand then slowly raised to about 150° C. After about one hour at about150° C., the N₂ atmosphere was removed and a vacuum was applied. Afterabout one hour, the vacuum was removed, the N₂ atmosphere wasre-established, and the temperature was lowered to about 135° C. Whenthe temperature reached about 135° C., about 71.5 grams (0.480 moles) ofdimethylaminobenzaldehyde³ were added and heated, under N₂, for aboutone hour. The N₂ atmosphere was then removed, the temperature wasincreased to about 150° C., and a vacuum was applied. After about onehour, the vacuum was removed and the reaction product was poured intoaluminum pans and allowed to cool and solidify. The final product was ayellow solid at room temperature. A sample of the final product wasdissolved in toluene, and was determined to have a spectral strength ofabout 69,560 (milliliters*Absorbance Units/gram) at a lambda_(max) of407 nm. The spectral strength was measured using a Perkin Elmer Lambda2S UV/VIS spectrophotometer.¹ ARMEEN 18D FLK—Octadecyl amine available from AKZO NOBEL ChemicalsInc. of McCook, Ill.² Methyl cyanoacetate—available from Aldrich Chemicals of Milwaukee,Wis.³ Dimethylaminobenzaldehyde—available from Aldrich Chemicals ofMilwaukee, Wis.

EXAMPLE 2

About 600.0 grams of stearyl stearamide⁴, about 432.0 grams (1.674moles) of octylphenol ethoxylate⁵, about 252.0 grams (0.696 moles) ofhydroabietyl alcohol⁶, and about 273.0 grams (0.52) moles of C-32 linearalcohol⁷ were mixed in a 3 L four-neck resin kettle equipped with aTrubore stirrer, N₂ atmosphere, addition funnel (200 mL), andthermocouple-temperature controller. This mixture was heated to 125° C.and agitation begun when all components were molten (at approximately100° C.). To the mixture, and about 334.2 grams (1.505 moles) ofisophorone diisocyanate⁸ was added over approximately five minutesthrough the addition funnel. About 0.66 grams of dibutyltindilaurate⁹was added and the reaction mixture heated to about 150° C. After abouttwo hours at about 150° C., additional amounts of about 45.0 grams(0.174 moles) of octylphenol ethoxylate, about 45.0 grams (0.124 moles)of hydroabietyl alcohol, about 45.0 grams (0.086 moles) of C-32 linearalcohol, and about 0.05 grams of dibutyltindilaurate were added and thereaction mixture maintained at about 150° C. for about two hours. AFourier transform infrared spectrum (FT-IR spectrum) of the reactionproduct was obtained to insure that all of the isocyanate functionalitywas consumed. The absence (disappearance) of a peak at ˜2285 cm⁻¹ (NCO)and the appearance (or increase in magnitude) of peaks at ˜1740-1680cm⁻¹ and ˜1540-1530 cm⁻¹ corresponding to urethane frequencies were usedto confirm this. The final mixed urethane product was then poured intoaluminum molds and allowed to cool and harden. The resulting product wasa solid at room temperature and characterized by a viscosity of about14.92 cPs as measured by a Ferranti-Shirley cone-plate viscometer atabout 140° C. ≠⁴ S-180—stearyl stearamide available from Witco Corp.,Greenwich, Conn. ≠⁵ IGEPAL CA-210—octylphenol ethoxylate, available fromRhone-Poulenc Co., Cranbury, N.J. ≠⁶ Abitol E—hydroabietyl alcoholavailable from Hercules Inc. of Wilmington, Del. ≠⁷ UNILIN 425—C-32linear alcohol available from Baker petrolite of tulsa, Okla. ≠⁸Desmodur I—isophorone diisoyanate available from Bayer corp. ofPittsburgh, Pa. ≠⁹ FASCAT 4202—dibutyltindilaurate available from Elfatochem North America Inc. of Philadelphia, Pa.

EXAMPLE 3

About 345.0 grams of the material from Example 2, about 125.0 grams ofLawter SA-3850 (Lawter International, Inc. or Northbrook, Ill.), andabout 10.0 grams of the yellow colorant from Example 1 were combined ina one-liter stainless steel beaker. The materials were melted togetherat a temperature of about 125° C. in an oven, then blended by stirringin a temperature controlled mantle at about 125° C. for about one-halfhour to form a yellow ink. The yellow ink was filtered through a heatedMott apparatus (available from Mott Metallurgical) using a 2 micronfilter and a pressure of about 15 psi. The filtered phase change ink waspoured into molds and allowed to solidify to form ink sticks. The finalink product had a viscosity of about 11.44 cPs as measured by aFerranti-Shirley cone-plate viscometer at about 140° C. The product hada spectral strength of 1400 (milliliters*Absorbance Units/gram) at alambda_(max) of 407 nm when dissolved in toluene. The spectral strengthwas measured using a Perkin Elmer Lambda 2S UV/VIS spectrophotometer.

The ink was tested in a Tektronix PHASER™ 340 printer (which uses anoffset transfer printing system), and was found to provide images ofgood color, print quality and durability.

EXAMPLE 4

A 100 mL one-neck flask was equipped with a magnet and placed in asilicone oil bath on a hot plate/magnetic stirrer. The flask wasequipped with a vacuum adapter and configured to be filled with an N₂atmosphere. About 10.0 grams of stearyl amine¹⁰ and about 12.5 gramsINTRATHERM YELLOW P346™¹¹ were mixed in the flask. The mixture washeated to about 95° C. in an N₂ atmosphere, at which time it becamemolten and agitation was begun. After about 0.5 hours at about 95° C.,the temperature was increased to about 105° C. and held forapproximately four hours. Bubbles were observed evolving from thereaction mixture for several hours. The temperature was then increasedto about 110° C. and held for about six hours. The N₂ addition was thenstopped, a vacuum was introduced to the reaction vessel, and thetemperature was maintained at about 110° C. After about 30 minutes, thevacuum was removed, N₂ reintroduced, about 80 mL of toluene was added,and the reaction mixture allowed to cool to room temperature withstirring.¹⁰ ARMEEN 18D FLK—Octadecyl aminc available from AKZO NOBEL ChemicalsInc. of McCook, Ill.¹¹ INTRATHERM YELLOW P-346—Disperse Yellow 238 available from Cromptonand Knowles Colors, Inc., Charlotte, N.C.

The reaction product in toluene was then poured into a 600 mL coarsefrit Buchner funnel containing a toluene slurry of silica gel¹² andattached to a 1-liter vacuum flask. About 500 mL of toluene was elutedthrough the silica gel and subsequently removed via rotary evaporation.This toluene elution step was repeated two additional times, and a finaltime with acetone. A total of four 500 mL fractions were collected andconcentrated. Thin layer chromatography (TLC) on reversed phase platesof the four fractions was performed (using methanol as an eluent) andsimultaneously compared with the starting dye. The third fraction showedthe highest percentage of the desired, purified product. The purifiedreaction product (referred to hereafter as stearyl-modified INTRATHERMYELLOW P-346™) was a deep orange wax. The spectral strength of thepurified product was determined in toluene to be 33,400(milliliters*Absorbance Units/gram) at 414 nm. The peak width at halfheight was determined to be 110 nm.¹² Silica Gel—70-230 mesh column chromatography grade available fromAldrich Chemical Co., Milwaukee, Wis.

Image Stability Characterization of the Stearyl-Modified INTRATHERMYELLOW P-346™

Two inks were prepared utilizing a common phase change ink carrier. Theonly difference between the two inks was that one of the inks usedINTRATHERM YELLOW P-346™ as a colorant, and the other ink used thestearyl-modified INTRATHERM YELLOW P-346™ of Example 4 as a colorant.The dye proportions in the two inks were adjusted to normalize thespectral strength. The two inks were printed on a PHASER™ 600 printerand the relative performance of the inks was compared by several testmethods. Results of these tests are tabulated below.

A. Color Print Test

The ink comprising stearyl-modified INTRATHERM YELLOW P-346™ as acolorant gave a slightly reddish yellow solid fill of high chromaticity.The color space was determined and is listed below in Table 1. TABLE 1COLOR L* a* b* Cyan 50.66 −19.91 −42.91 Magenta 49.48 73.53 −20.17Yellow 82.00 3.12 94.73 Black 24.12 0.81 −0.44 Red 46.51 58.15 39.39Green −38.91 24.47 11.2 Blue 26.44 28.97 −44.38

B. Diffusion

The extent of dye diffusion was determined by using the CIELABcolor-difference formula¹³ for measurements of the same test panelbefore and after aging 72 hours in a 45° C. oven. The resulting colordifference values (ΔE) are summarized in Table 2, which lists diffusionobserved for two types of prints: unlaminated and laminated. Test panelscontaining small amounts of the diffusing color surrounded by largeamounts of a second color have been observed to be most sensitive to dyediffusion. The proportion of the primary process colors in each testpanel is shown in column 1 of Table 2. Data obtained utilizingcommercially available INTRATHERM YELLOW P-346™ is listed under thecategory “Unmodified” in Table 2, and data obtained from thestearyl-modified INTRATHERM YELLOW P-346™ of Example 4 is listed underthe category “Modified” in Table 2. The data in Table 2 show that thestearyl-modified INTRATHERM YELLOW P-346™ has about a 56% improvementwhen unlaminated, and about a 28% improvement when laminated relative totest panels containing unmodified INTRATHERM YELLOW P-346™.¹³ ASTM Method D 2244-89Standard Test Method for Calculation of ColorDifferences from Instrumentally Measured Color Coordinates.TABLE 2 DIFFUSION TEST RESULTS (ΔE, relative to initial colormeasurement) Test Panel Composition Unlaminated Laminated C/M/YUnmodified Modified Unmodified Modified  20/0/0 0.3 0.1 n/a* 0.3 20/100/0 1.8 0.8 2.6 2.9  20/0/100 1.6 1.6 1.6 1.4 100/20/0 5.4 5.7n/a* 3.0  0/20/0 1.5 1.0 4.1 2.5  0/20/100 6.4 3.8 3.4 2.1 100/0/20 19.510.0 n/a* 14.3  0/100/20 14.3 8.5 16.2 11.7  0/0/20 2.7 0.5 24.9 18.3*Means not available

C. Blooming

Blooming was tested by placing a printed solid fill image in a 60° C.oven for seven days. Prior to placement in the oven, the bottom sectionof the image was impressed with fingerprint oil. In addition, a strip oftransparent tape was placed across the lower margin. Blooming could beobserved in the sample comprising commercially available (i.e.,unmodified) INTRATHERM YELLOW P-346™ after seven days, whereas thesample comprising stearyl-modified INTRATHERM YELLOW P-346™ did notexhibit significant blooming after the same period of time. In addition,a white facial tissue could be gently wiped across the sample comprisingunmodified INTRATHERM YELLOW P-346™. This was not observed whenperformed with the sample comprising stearyl-modified INTRATHERM YELLOWP-346™.

D. Carryover of Sublimation onto Facing Sheet

The samples utilized for the blooming test (described above) were alsoutilized for testing carryover of sublimation onto a facing sheet. Anunprinted sheet was provided over and in facing relation to the samples.Examination of the facing sheet revealed a noticeable migration ofyellow dye from the sample comprising unmodified INTRATHERM YELLOWP-346™ after seven days at 60° C., and revealed no migration of yellowdye from the sample comprising stearyl-modified INTRATHERM YELLOWP-346™.

E. Tape Diffusion

Printed samples comprising stearyl-modified INTRATHERM YELLOW P-346™were compared to printed samples comprising unmodified INTRATHERM YELLOWP-346™ for diffusion under transparent tape. Such comparison showed thatthe samples comprising stearyl-modified INTRATHERM YELLOW P-346™ hadabout a 50% improvement relative to the samples comprisingstearyl-modified INTRATHERM YELLOW P-346™ (i.e., less colorantmigration), as determined by visual inspection.

1. A compound having the formula:

wherein R₁, Z, and the carbonyl can be comprised by a common ring,wherein R₁ comprises a chromophore that absorbs light from the visiblewavelength range, wherein Z is an atom or group of atoms, said atom orgroup of atoms including at least one atom selected from the groupconsisting of C, O, N, and S, and wherein n is an integer that is atleast
 39. 2. A compound according to claim 1 wherein n is not more than299.
 3. A compound according to claim 1 wherein Z is NH.
 4. A compoundaccording to claim 1 wherein Z isN—(CH₂)_(y)CH₃ wherein y is an integer of from 0 to 300 and can be thesame as or different from n.
 5. A compound according to claim 1 whereinthe R₁ and the carbonyl together comprise a chemical group selected fromthe group consisting of ester, lactone, amide, lactam, and imide.
 6. Acompound according to claim 1 having the formula

wherein R₅₀, R₅₁, R₅₂, and R₅₃ are selected from the group consisting ofhydrogen, halogens, hydroxy groups, alkoxy groups, trifluoromethylgroups, and alkyl groups, and can be the same as one another ordifferent from one another, and wherein at least one of R₇ and R₈comprises a chain having the formula

wherein j is an integer from 0 to about 300, wherein the representationof “(Q,H)” indicates that either a group Q or a hydrogen can be in theshown positions, wherein the group Q is either an alkyl group or an arylgroup, and wherein Q can vary amongst different alkyl and aryl groupswithin the chain.
 7. A compound according to claim 1 having the formula

wherein at least one of R₇ and R₈ comprises a chain having the formula

wherein j is an integer from 0 to about 300, wherein the representationof “(Q,H)” indicates that either a group Q or a hydrogen can be in theshown positions, wherein the group Q is either an alkyl group or an arylgroup, and wherein Q can vary amongst different alkyl and aryl groupswithin the chain.
 8. A compound according to claim 1 having the formula

wherein R₈₀, R₈₁, R₈₂, R₈₃, R₈₄, R₈₅, R₈₆, R₈₇, R₈₈, and R₈₉ areselected from the group consisting of hydrogen, halogens, hydroxygroups, alkoxy groups, trifluoromethyl groups, and alkyl groups, and canbe the same as one another or different from one another, and whereinR₃, R₄, R₅, and R₆ are selected from the group consisting of hydrogenand carbon-containing materials and can be the same as one another ordifferent from one another.
 9. A compound according to claim 1 havingthe formula

wherein R₃, R₄, R₅, and R₆ are selected from the group consisting ofhydrogen and carbon-containing materials and can be the same as oneanother or different from one another.
 10. A compound having theformula:

wherein R₆₀, R₆₁, R₆₂, R₆₃, R₆₄, R₆₅, R₆₆, R₆₇, R₆₈, R₆₉, R₇₀, and R₇₁are selected from the group consisting of hydrogen, halogens, hydroxygroups, alkoxy groups, trifluoromethyl groups, and alkyl groups, and canbe the same as one another or different from one another, wherein Dcomprises carbon, sulfur, phosphorus, or nitrogen, wherein R₁₀, R₁₁,R₁₂, R₁₃, R₁₄, and R₁₅ are selected from the group consisting ofhydrogen and carbon-containing materials and can be the same as oneanother or different from one another, wherein Z₁, Z₂, and Z₃ can be thesame as one another or different from one another and comprise S, O, C,or N, and wherein a, b, and c can be the same as one another ordifferent from one another and are integers that are at least
 1. 11. Acompound according to claim 10 wherein R₆₀, R₆₁, R₆₂, R₆₃, R₆₄, R₆₅,R₆₆, R₆₇, R₆₈, R₆₉, R₇₀, and R₇₁ are hydrogen.
 12. A compound accordingto claim 10 wherein D is nitrogen and is in a cationic form.
 13. Acompound according to claim 10 wherein at least one of R₁₀, R₁₁, R₁₂,R₁₃, R₁₄, and R₁₅ comprises a chain having the formula

wherein j is an integer from 0 to about 300, wherein the representationof “(Q,H)” indicates that either a group Q or a hydrogen can be in theshown positions, wherein the group Q is either an alkyl group or an arylgroup, and wherein Q can vary amongst different alkyl and aryl groupswithin the chain.
 14. A compound according to claim 10 wherein each ofR₁₀, R₁₁, R₁₂, R₁₃, R₁₄, and R₁₅ comprises a chain having the formula

wherein j is an integer from 0 to about 300, wherein the representationof “(Q,H)” indicates that either a group Q or a hydrogen can be in theshown positions, wherein the group Q is either an alkyl group or an arylgroup, and wherein Q can vary amongst different alkyl and aryl groupswithin the chain.
 15. A compound according to claim 10 wherein each OfZ₁, Z₂, and Z₃ is NH.
 16. A compound comprising at least two segments ofthe formula shown below joined to one another through a common atom ormulti-atom structure:

wherein R₇₃, R₇₄, R₇₅, and R₇₆ are selected from the group consisting ofhydrogen, halogens, hydroxy groups, alkoxy groups, trifluoromethylgroups, and alkyl groups, and can be the same as one another ordifferent from one another, wherein R₂₀ and R₂₁ are selected from thegroup consisting of hydrogen and carbon-containing materials and can bethe same as one another or different from one another, wherein Z₅comprises at least one of C, S, O, or N, wherein b comprises an integerthat is at least 1, the integer b being the same or different amongstthe different segments, Z₅ being the same or different amongst thedifferent segments, and the groups R₂₀ and R₂₁ being the same ordifferent amongst the different segments.
 17. A compound according toclaim 16 wherein R₇₃, R₇₄, R₇₅, and R₇₆ are hydrogen.
 18. A compoundaccording to claim 16 wherein the compound comprises at least three ofthe segments having the shown formula.
 19. A compound according to claim16 wherein the at least two segments are joined through a common atom,said common atom being either carbon, sulfur, phosphorus, or nitrogen.20. A compound according to claim 1 having the formula

wherein R₅₀, R₅₁, R₅₂, and R₅₃ are selected from the group consisting ofhydrogen, halogens, hydroxy groups, alkoxy groups, trifluoromethylgroups, and alkyl groups, and can be the same as one another ordifferent from one another, and wherein at least one of R₇ and R₈comprises a chain having the formula

wherein j is an integer from 0 to about 300, wherein the representationof “(Q,H)” indicates that either a group Q or a hydrogen can be in theshown positions, wherein the group Q is either an alkyl group or an arylgroup, and wherein Q can vary amongst different alkyl and aryl groupswithin the chain, wherein n is at least
 17. 21. A compound according toclaim 1 having the formula

wherein at least one of R₇ and R₈ comprises a chain having the formula

wherein j is an integer from 0 to about 300, wherein the representationof “(Q,H)” indicates that either a group Q or a hydrogen can be in theshown positions, wherein the group Q is either an alkyl group or an arylgroup, and wherein Q can vary amongst different alkyl and aryl groupswithin the chain, wherein n is at least 17.